Telomerization by free-radical mercaptan chain transfer. IV. Effects of structure,solvent and initiator variation on the stereochemistry of acrylate ester–mercaptan telomers

Chain-transfer constants for radicals one to five units in length were determined for the methyl acrylate–isopropanethiol system. Effects of varying ester alkyl group, mercaptan solvent and initiator on three-unit diastereomer ratio were also investigated. It was found that the proportion of syndiotactic isomer increased as the size of either the ester alkyl group or the mercaptan increased, the latter result being equivalent to a penultimate effect. Polar solvents, on the other hand, favored the formation of the isotactic form. This effect was observed in the free-radical telomerization and to an even greater degree in the base-initiated anionic telomerization. Possible reasons for solvent effects are discussed.     

Self-induced transparency in diblock copolymer dispersions

We report on the versatile effect of weak red laser light impinging on diblock copolymer [poly(isoprene-b-styrene)] dispersions in two selective solvents for each block. In the strongly scattering but transparent micellar solutions in hexane (a good solvent for polyisoprene), higher refractive index copolymer-rich fibers were formed. In the turbid dispersions of the same copolymer in ethyl acetate (a good solvent for polystyrene), the effect of self-induced transparency was observed. A two-step patterning mechanism caused the generation of a transparent microchannel, increasing light transmission. The analogy between the current effect and that observed in homopolymer polyisoprene solutions in different solvents is discussed toward an understanding of the unanticipated light-soft-matter interaction.     

Synthesis of macrocyclic ligands containing the indole ring system

2,7-Diformyl-3-methyl-4,6-dimethoxyindole (6) has been synthesized and converted by metal template reactions into the macrocyclic complexes (10–12).     

Determination of boron in titanium alloys by means of ion exchange

There is need for a rapid method for the determination of moderate amounts of boron in titanium alloys. In this paper a method is proposed which uses ion exchange. The method is applicable to titanium alloys containing 0.025 to 1 per cent. boron. One or two grams of the sample are dissolved in hydrochloric acid, and the titanium and boron are oxidized with nitric acid. The bulk of the titanium is removed by a cation exchanger. A calcium carbonate separation is made to remove the residual titanium and adjust the acidity. The boron is then titrated with sodium hydroxide, after the addition of mannitol. None of the elements found in commercial titanium alloys interferes with the method.     

Efficient broadband silicon-on-insulator grating coupler with low backreflection

We design and fabricate an efficient broadband grating coupler on a 400 nm thick silicon-on-insulator wafer. The measured coupling loss is 3 dB when coupling to a single-mode fiber at 1310 nm wavelength with TE polarization. The spectral FWHM and backreflection are determined to be 58 nm and -27 dB, respectively.     

The crystal structure of tetrakis(methyldiphenylphosphine)iridium(I) tetrafluoroborate with cyclohexane of solvation: Ir[P(C6H5)2CH3]4BF4 - C6H12

The crystal structure of tetrakis(methyldiphenylphosphine)iridium(I) tetrafluoroborate with cyclohexane of solvation, [Ir(PPh₂Me)₄]BF₄·C₆H₁₂, has been determined from a three-dimensional X-ray analysis. The compound has been analysed in space group C₂/c of the monoclinic system. There are twelve molecules (i.e. 1.5 molecules per asymmetric unit) in a cell of dimensions a = 36.804(8), b = 22.93(2), c = 21.676(4) Å, β = 121.41(1)°. Block-diagonal least-squares refinement has given a final R-factor of 0.060 for 7905 reflections having I > 3σ(I).The structure consists of two crystallographically distinct, but structurally similar molecules, one on a general position and one on a crystallographic two-fold axis. The phosphine ligands around the iridium atoms are in a very distorted square-planar arrangement. The reactions of the cation axe discussed in terms of this structure.     

The gas-phase ozonolysis of unsaturated volatile organic compounds in the troposphere

The gas-phase reactions of ozone with unsaturated hydrocarbons are significant sources of free radical species (including *OH) and particulate material in the Earth's atmosphere. In this tutorial review, the kinetics, products and mechanisms of these reactions are examined, starting with a discussion of the original mechanism proposed by Criegee and following with a summary presentation of the complex, free radical-mediated reactions of carbonyl oxide (Criegee) intermediates. The contribution of ozone-terpene reactions to the atmospheric burden of secondary organic aerosol material is also discussed from the viewpoint of the formation of non-volatile organic acid products from the complex chemistry of ozone with alpha-pinene. Throughout the article, currently accepted understanding is supported through the presentation of key experimental results, and areas of persistent or new uncertainty are highlighted.     

Ruthenium complexes containing bis-benzimidazole derivatives as a new class of apoptosis inducers

A series of ruthenium complexes containing bis-benzimidazole derivatives have been synthesized and identified as able to target mitochondria and induce caspase-dependent apoptosis in cancer cells through superoxide overproduction.